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The development of variational density functional theory approaches to excited electronic states is impeded by limitations of the commonly used self-consistent field (SCF) procedure. A method based on a direct optimization approach as well…

Chemical Physics · Physics 2022-11-09 Gianluca Levi , Aleksei V. Ivanov , Hannes Jónsson

Density functional theory (DFT) based modeling of electronic excited states is of importance for investigation of the photophysical/photochemical properties and spectroscopic characterization of large systems. The widely used linear…

Chemical Physics · Physics 2021-05-11 Diptarka Hait , Martin Head-Gordon

State-specific complete active space self-consistent field (SS-CASSCF) theory has emerged as a promising route to accurately predict electronically excited energy surfaces away from molecular equilibria. However, its accuracy and…

Chemical Physics · Physics 2024-02-21 Sandra Saade , Hugh G. A. Burton

Most realistic calculations of moderately correlated materials begin with a ground-state density functional theory (DFT) calculation. While Kohn-Sham DFT is used in about 40,000 scientific papers each year, the fundamental underpinnings are…

Strongly Correlated Electrons · Physics 2022-09-26 Kieron Burke , John Kozlowski

The Hohenberg-Kohn theorem of the density functional theory is extended by modifying the Levy constrained-search formulation. The new theorem allows us to choose arbitrary physical quantities as the basic variables which determine the…

Condensed Matter · Physics 2009-11-10 M. Higuchi , K. Higuchi

State-of-the-art methods for calculating neutral excitation energies are typically demanding and limited to single electron-hole pairs and their composite plasmons. Here we introduce excitonic density-functional theory (XDFT) a…

Chemical Physics · Physics 2023-01-09 Subhayan Roychoudhury , Stefano Sanvito , David D. O'Regan

In contrast to the original Kohn-Sham (KS) formalism, we propose a density functional theory (DFT) with fractional orbital occupations for the study of ground states of many-electron systems, wherein strong static correlation is shown to be…

Chemical Physics · Physics 2015-06-03 Jeng-Da Chai

A recent work [arXiv:2401.04685] has merged $N$-centered ensembles of neutral and charged electronic ground states with ensembles of neutral ground and excited states, thus providing a general and in-principle exact (so-called extended…

Strongly Correlated Electrons · Physics 2024-05-14 Filip Cernatic , Emmanuel Fromager

Orbital-optimized density functional theory (DFT) has emerged as an alternative to time-dependent (TD) DFT capable of describing difficult excited states with significant electron density redistribution, such as charge-transfer, Rydberg,…

Chemical Physics · Physics 2025-01-22 Hanh D. M. Pham , Rustam Z. Khaliullin

Following a recent work [E. Fromager, J. Phys. Chem. A 2025, 129, 4, 1143-1155] on the ensemble density functional theory (DFT) of excited electronic energy levels, we derive in this paper the ensuing static linear response theory, thus…

Chemical Physics · Physics 2025-09-26 Lucien Dupuy , Emmanuel Fromager

We introduce an orbital free electron density functional approximation based on alchemical perturbation theory. Given convergent perturbations of a suitable reference system, the accuracy of popular self-consistent Kohn-Sham density…

Chemical Physics · Physics 2020-05-27 Guido Falk von Rudorff , O. Anatole von Lilienfeld

We propose a new method of calculating electronically excited states that combines a density functional theory (DFT) based ground state calculation with a linear response treatment that employs approximations used in the time-dependent…

Chemical Physics · Physics 2016-05-11 Robert Rüger , Erik van Lenthe , Thomas Heine , Lucas Visscher

We present excited states density functional theory (DFT) to calculate band gap for semiconductors and insulators. For the excited states exchange-correlation functional, we use a simple local density approximation (LDA) like functional and…

We present a novel joint time-dependent density-functional theory for the description of solute-solvent systems in time-dependent external potentials. Starting with the exact quantum-mechanical action functional for both electrons and…

Materials Science · Physics 2012-02-16 Johannes Lischner , T. A. Arias

Accurate modeling of warm and hot dense matter is challenging in part due to the multitude of excited states that must be considered. In thermal density functional theory, these excited states are averaged over to produce a single,…

Plasma Physics · Physics 2024-05-16 C. E. Starrett , T. Q. Thelen , C. J. Fontes , D. A. Rehn

In order to study electron-transfer mediated chemical processes on a metal surface, one requires not one but two potential energy surfaces (one ground state and one excited state) as in Marcus theory. In this letter, we report that a novel,…

Chemical Physics · Physics 2023-03-22 Junhan Chen , Joseph Subotnik

In this paper we demonstrate the performance of several density-based methods in predicting the inversion of S$_1$ and T$_1$ states of a few N-heterocyclic fused ring molecules (popularly known as INVEST molecules) with an eye to identify a…

Chemical Physics · Physics 2024-08-12 Shamik Chanda , Subhasish Saha , Sangita Sen

The development of kinetic energy functional (KEF) is known as one of the most difficult subjects in the electronic density functional theory (DFT). In particular, the sound description of chemical bonds using a KEF is a matter of great…

Chemical Physics · Physics 2025-03-03 Hideaki Takahashi

In this work we establish a density-functional reformulation of coupled matter-photon problems subject to general external electromagnetic fields and charge currents. We first show that for static minimally-coupled matter-photon systems an…

Quantum Physics · Physics 2017-08-07 M. Ruggenthaler

Spectroscopies that probe electronic excitations from core levels into unoccupied orbitals, such as X-ray absorption spectroscopy and electron energy loss spectroscopy, are widely used to gain insight into the electronic and chemical…

Materials Science · Physics 2022-09-12 Marcus Annegarn , Juhan Matthias Kahk , Johannes Lischner